Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

REE, Ba, and Sr abundances and Sr, Nd, and Ce isotope ratos of ODP Hole 110-504B basalts

Abundances of rare earth elements (REE), Ba, and Sr and isotopic ratios of Sr, Nd, and Ce were determined for six samples of basalts drilled at Hole 504B on Leg 111 of the Ocean Drilling Program. Analyses found that these basalts are the most depleted in Sr, Ba, and light REE among mid-ocean ridge basalts (MORB); Ba depletion is especially notable. On the other hand, Sr, Nd, and Ce isotopic ratios for basalts from Hole 504B are within the range of typical MORB values.

Age profiles and isotopes d18O and d13C in Globigerina angiporoides and Oridorsalis umbonatus at DSDP Site 90-593 and Holes 12-111, 29-277 and 90-592

The late Eocene through earliest Miocene stable-isotope composition of southwest Pacific microfossils has been examined in a traverse of high-quality sedimentary sequences ranging from subantarctic (DSDP Site 277) through temperate regions (DSDP Sites 592 and 593). Changes in oxygen-isotope values, measured in benthic and planktonic foraminifers, document the Oligocene development and strengthening of latitudinal thermal zonation from water masses with broad temperature gradients during the Eocene to the steeper gradients and more distinct latitudinally distributed surface water-mass belts of the Neogene. The oxygen-isotope records can be divided into three intervals: late Eocene, early Oligocene, and middle to late Oligocene. Each interval represents a successive stage in the evolution of latitudinal thermal gradients between subantarctic and temperate regions in the Southern Hemisphere. During the late Eocene, oxygen-isotope values at subantarctic Site 277 were similar to those at temperate Sites 592 and 593. The isotope values suggest that, although the inferred paleotemperatures at Site 277 are slightly cooler on average than those at the temperate sites, there is no evidence for a major thermal boundary between the regions at this time. All three sites record the well-known oxygen-isotope enrichment of about 1 per mil in both planktonic and benthic foraminifers in close association with the Eocene/Oligocene boundary. In contrast to the earliest Oligocene enrichments in the planktonic and benthic oxygen-isotope composition at Site 277, more northern Sites 592 and 593 exhibit a depletion through the early-middle Oligocene. This documents the beginning of thermal segregation as subantarctic waters cooled relative to those at temperate latitudes. During the Oligocene, this surface-water differentiation continued, as measured by planktonic d18O values. The oxygen-isotope records of the benthic foraminifers also began to diverge in the earliest Oligocene. The most enriched oxygen-isotope values in all records cluster in the middle Oligocene, marked by oscillating episodes of enrichments >0.5 per mil occurring most prominently in the subantarctic record of Site 277. These values can be interpreted as recording either the coldest oceanic temperatures of the Paleogene and/or accumulations of Antarctic ice. After this interval, latitudinal thermal differentiation developed rapidly during the middle Oligocene, especially in the surface waters which actually warmed in temperate areas. If the enriched Oligocene oxygen-isotope values indicate that ice had accumulated, this ice must have disappeared by the early Miocene, when depleted oxygen-isotope values suggest very warm conditions. The data presented in this chapter document the progressive increase of latitudinal temperature gradients from the late Eocene through the late Oligocene. This pattern of increasing isotopic offset between latitudinally distributed southwest Pacific sites is linked to the establishment and strengthening of the Circum-Antarctic Current, previously considered to have developed during the middle to late Oligocene. The intensification of this current system progressively decoupled the warm subtropical gyres from cool polar circulation, in turn leading to increased Antarctic glaciation.

Oxygen isotope composition of planktonic foraminifer Globigerinoides ruber in sediment core GeoB1413 from the eastern edge of the South Atlantic central gyre

Die Paläozeanographie versucht die Klimageschichte des Quartärs zu rekonstruieren und die Zusammenhänge zwischen Klimaänderungen und ozeanischer Zirkulation besser zu verstehen. Ein wichtiges Hilfsmittel stellen die planktischen Foraminiferen dar. Die Analyse planktischer Foraminiferengemeinschaften hat gezeigt, daß die Verbreitung dieser Protozoa durch die Umweltbedingungen in den Oberflächenwasserströmen bestimmt wird (BoLTOVSKOY, 1969; CIFELLI& BENIER, 1976; OTIENS, 1991). Durch ihre Ablagerung und Erhaltung am Meeresboden speichern sie diese Informationen und bilden einen Indikator für Wassermassen und Oberflächenwassertemperaturschichtung. Zeitliche und räumliche Veränderungen der Faunenvergesellschaftungen und der Verhältnisse stabiler Sauerstoff- und Kohlenstoffisotope einzelner Foraminiferenarten haben damit einen maßgeblichen Beitrag zur Kenntnis der spätquartären Temperatur- und Zirkulationsänderungen der Oberflächenströme geliefert (SHACKLETON & OPDYKE, 1973; BE et al., 1976; RUDDIMAN & McooYRE, 1976; VINCENT & BERGER, 1981; CLIMAP, 1981; RA VELO et al., 1990). Mit Hilfe der planktischen Foraminiferen soll diese Arbeit einen Beitrag zur Rekonstruktion der spätquartären Ozeanographie des Südatlantiks liefern. Die Oberflächenströme des Südatlantiks sind das Bindeglied im Wärmeaustausch zwischen niederen und hohen Breiten. Durch den Südäquatorialstrom (SEC) werden warme Wassermassen, die sich aufgrund der hohen Sonneneinstrahlung im tropischen Atlantik gebildet haben, in den Nordatlantik transportiert. Die Wärme wird im Nordatlantik unter Bildung des Nordatlantischen-Tiefenwassers (NADW) an die Atmosphäre abgegeben. Durch dieses Ereignis wird maßgeblich das nordeuropäische Klima beeinflußt (BROECKER & DENTON, 1989). Die Intensität des SEC wird durch den saisonal variierenden SE-, NE-Passat gesteuert, der hauptsächlich durch die Präzession der geneigten Erdachse bzw. durch die Insolation auf der Nordhalbkugel kontrolliert wird (Mc OOYRE et aI., 1989; MOLFINO & Mc INTYRE, 1990). Der SEC fließt entlang des Äquators von Ost nach West und kalte, nährstotfreiche, tiefere Wassermassen (Südatlantisches-Zentralwasser (SACW)) steigen vor allem im Osten auf und erzeugen das hochproduktive äquatoriale Auftriebsgebiet. Im Osten ist der Temperaturgradient in der Wassersäule steiler, und die Thermoklinentiefe nimmt von Ost nach West zu. Die Lage der Thermokline ist damit ein wesentlicher Faktor, der den Wärmehaushalt im Atlantik mitbestimmt. So wird z. B. im äquatorialen Auftriebsgebiet und im Auftriebsgebiet des küstennahen Benguela-Stroms, wo die Thermoklinentiefe durch aufsteigende kalte Wassermassen gering ist, eine Wärmezunahme von 100 W/qm im Wärmehaushalt erreicht (PETERSON & STRAMMA, 1991). Zur spätquartären Rekonstruktion des Wärmeflusses und der Oberflächenzirkulation im Südostatlantik ist es daher wichtig, auch die zeitlichen und räumlichen Veränderungen tieferer Wasserschichten (bis 300 m) zu erfassen.

Stable isotope analyses of Cretaceous sediment samples

We report the sulfur and oxygen isotope composition of sulfate (d34SSO4 and d18OSO4, respectively) in coexisting barite and carbonate-associated sulfate (CAS), which we use to explore temporal variability in the marine sulfur cycle through the middle Cretaceous. The d34SSO4 of marine barite tracks previously reported sulfur isotope data from the tropical Pacific. The d18OSO4 of marine barite exhibits more rapid and larger isotopic excursions than the d34SSO4 of marine barite; these excursions temporally coincide with Ocean Anoxic Events (OAEs). Neither the d34SSO4 nor the d18OSO4 measured in marine barite resembles the d34SSO4 or the d18OSO4 measured in coexisting CAS. Culling our data set for elemental parameters suggestive of carbonate recrystallization (low [Sr] and high Mn/Sr) improves our record of d18OSO4 in CAS in the Cretaceous. This suggests that the CAS proxy can be impacted by carbonate recrystallization in some marine sediments. A box model is used to explore the response of the d34SSO4 and d18OSO4 to different perturbations in the marine biogeochemical sulfur cycle. We conclude that the d34SSO4 in the middle Cretaceous is likely responding to a change in the isotopic composition of pyrite being buried, coupled possibly with a change in riverine input. On the other hand, the d18OSO4 is likely responding to rapid changes in the reoxidation pathway of sulfide, which we suggest may be due to anoxic versus euxinic conditions during different OAEs.

Os isotope record of ODP Site 159-959

The known temporal relationship between the benthic foraminiferal d18O record and the marine Os isotope record is used to reinterpret the absolute chronology and paleoceanographic context of an episode of organic carbon burial on the West African margin Ocean Drilling Program (ODP) Site 959. Although organic-rich sediments require significant corrections for in situ decay of 187Re to 187Os, these results demonstrate the utility of the marine Os isotope record for chemostratigraphic correlation of organic-rich sediments that are devoid of age diagnostic microfossils with pelagic carbonate sequences. Revision of the ODP Site 959 chronology shifts the age assignment of an interval of biosiliceous, organic-rich sediment deposition from the Oligocene to the late Eocene and earliest Oligocene, likely culminating with the first major glaciation of the Oligocene (Oi1). We speculate that enhanced organic carbon burial over much of the West African margin may have contributed to drawdown of atmospheric carbon dioxide before and during the Oi1 event and suggest that Os isotope chemostratigraphy provides a valuable tool for further exploring this possibility.

Stable isotope and geochemical analyses of sediment core SO164-17-2 from the southern Florida Straits

Modeling and proxy studies indicate that a reduction of Atlantic Meridional Overturning Circulation (AMOC) strength profoundly impacts temperatures and salinities in the (sub)tropical Atlantic, especially on subsurface levels. While previous studies focused on prominent periods of AMOC reduction during the last deglaciation, we aim to test whether similar reconfigurations of the subtropical hydrography occurred during the moderate climatic alterations punctuating the last interglacial, Marine Isotope Stage (MIS) 5. Here, we present temperature and salinity records from a Florida Straits core by combining d18O and Mg/Ca analyses on surface (Globigerinoides ruber, white) and deep-dwelling (Globorotalia crassaformis) foraminifera, covering MIS 5 in high resolution. The data reveal increasing salinities at intermediate depths during interglacial cooling episodes, decoupled from relatively stable surface conditions. This probably indicates the spatial expansion of saline Subtropical Gyre waters due to enhanced Ekman downwelling and might also point to a changed density structure and altered geostrophic balance in Florida Straits. Notably, these oceanographic alterations are not consistently occurring during periods of AMOC reduction. The data suggest that the expansion of gyre waters into Florida Straits was impeded by the increasing influence of Antarctic Intermediate Water (AAIW) from MIS 5.5 to ~107 kyr BP. Afterwards, increasingly positive benthic d13C values imply a recession of AAIW, allowing the temporary expansion of Gyre waters into Florida Straits. We argue that the inferred transient subtropical salt accumulation and warm pool expansion might have played a pivotal role in reinvigorating meridional overturning and dampen the severity of interglacial cold phases.

Stable isotope composition of Holocene benthic foraminifers from the Eastern Mediterranean Sea

Temporal and regional changes in paleoproductivity and paleoceanography in the eastern Mediterranean Sea during the past 12 kyr were reconstructed on the basis of the stable oxygen and carbon isotope composition of the epibenthic Planulina ariminensis and the shallow endobenthic Uvigerina mediterranea from three sediment cores of the Aegean Sea and Levantine Basin. The Younger Dryas is characterized by high d18O values, indicating enhanced salinities and low temperatures of deep water masses at all investigated sites. With the onset of the Holocene, d18O records show a continuous decrease towards the onset of sapropel S1 formation, mainly caused by a freshening and warming of surface waters at deep water formation sites. In the middle and late Holocene, the similarity of d18O values from the southern Aegean Sea and Levantine Basin suggests the influence of isotopically identical deep water masses. By contrast, slightly higher d18O values are observed the northern Aegean Sea, which probably point to lower temperatures of North Aegean deep waters. The epifaunal d13C records reveal clear changes in sources and residence times of eastern Mediterranean deep waters associated with period of S1 formation. Available data for the early and late phase of sapropel S1 formation and for the interruption around 8.2 kyr display drops by 0.5 and 1.5 per mil, indicating the slow-down of deep water circulation and enhanced riverine input of isotopically light dissolved inorganic carbon from terrestrial sources into the eastern Mediterranean Sea. The decrease in epifaunal d13C signals is particularly expressed in the southern Aegean Sea and Levantine Basin, while it is less pronounced in the northern Aegean Sea. This points to a strong reduction in deep water exchange rates in the southern areas, but the persistence of local deep water formation in the northern Aegean Sea. The d13C values of U. mediterranea records reveal temporal and regional differences in paleoproductivity during the past 12 kyr, with rather eutrophic and mesotrophic conditions in the North Aegean Sea and southeast Levantine Basin, respectively, while the South Aegean Sea is characterized by rather oligotrophic conditions. After S1 formation, increasing d13C values reflect a progressive decrease in surface water productivity in the eastern Mediterranean Sea during the middle and late Holocene. In the northern Aegean Sea, this time interval is marked by repetitive changes in organic matter fluxes documented by significant fluctuations in the d13C signal of U. mediterranea on millennial- to multi-centennial time scales. These fluctuations can be linked to short-term changes in river runoff driven by northern hemisphere climatic variability.

Age models of northern North Atlantic sediment cores

Benthic foraminiferal stable isotope records from four high-resolution sediment cores, forming a depth transect between 1237 m and 2303 m on the South Iceland Rise, have been used to reconstruct intermediate and deep water paleoceanographic changes in the northern North Atlantic during the last 21 ka (spanning Termination I and the Holocene). Typically, a sampling resolution of ~100 years is attained. Deglacial core chronologies are accurately tied to North Greenland Ice Core Project (NGRIP) ice core records through the correlation of tephra layers and changes in the percent abundance of Neogloboquadrina pachyderma (sinistral) with transitions in NGRIP. The evolution from the glacial mode of circulation to the present regime is punctuated by two periods with low benthic d13C and d18O values, which do not lie on glacial or Holocene water mass mixing lines. These periods correlate with the late Younger Dryas/Early Holocene (11.5-12.2 ka) and Heinrich Stadial 1 (14.7-16.8 ka) during which time freshwater input and sea-ice formation led to brine rejection both locally and as an overflow exported from the Nordic seas into the northern North Atlantic, as earlier reported by Meland et al. (2008). The export of brine with low ?13C values from the Nordic seas complicates traditional interpretations of low d13C values during the deglaciation as incursions of southern sourced water, although the spatial extent of this brine is uncertain. The records also reveal that the onset of the Younger Dryas was accompanied by an abrupt and transient (~200-300 year duration) decrease in the ventilation of the northern North Atlantic. During the Holocene, Iceland-Scotland Overflow Water only reached its modern flow strength and/or depth over the South Iceland Rise by 7-8 ka, in parallel with surface ocean reorganizations and a cessation in deglacial meltwater input to the North Atlantic.